3-phenyl-benzofuran-2-one diphosphate derivatives as stabilizers

ABSTRACT

The invention relates to a composition comprising an organic material susceptible to oxidative, thermal or light-induced degradation and a compound of formula I-P, I-O or I-M. Further embodiments are a compound of formula I-P, I-O or I-M, a process for protection of the organic material by the compound, the use of the compound against degradation of the organic material, an additive composition comprising the compound, processes for manufacturing the compound and an intermediate involved therein.

The current invention relates to a composition comprising an organicmaterial to be stabilized and a specific group of3-phenyl-benzofuran-2-one diphosphate derivatives as stabilizer. Aprocess for protection of the organic material by the specific group of3-phenyl-benzofuran-2-one diphosphate derivatives, the use of the latterone for stabilizing, the specific group of 3-phenylbenzofuran-2-onediphosphate derivatives, an additive composition comprising the latterone, processes for manufacturing the latter ones and intermediatesinvolved are further embodiments.

WO 80/01566 A discloses benzofuran-2-one or indolin-2-one derivatives asstabilizers.

U.S. Pat. No. 5,428,162 discloses as a stabilizer inter alia a3-phenyl-3H-benzofuran-2-one derivative, which is substituted by adi(C₁-C₆-alkyl)phosphonate group, e.g. compound No. 120(=2-[4-(5-methyl-2-oxo-3H-benzofuran-3-yl)phenoxy]ethyl2-diethoxyphosphorylacetate) as depicted:

WO 99/03915 A discloses blends of diphosphites and lactones having abase structure of 3-phenyl-benzofuran-2-one as stabilizers for polymers.

WO 2016/020322 A discloses 3-phenyl-benzofuran-2-one diphosphitederivatives as stabilizers, particularly for stabilization of polymers.An example of these derivatives is compound (102) as depicted:

While there are many stabilizers commercially used and significantlymore chemical classes of stabilizers are described, there is still aneed for further stabilizers. Beneath the performance as a stabilizeragainst degradation of the material to be stabilized, another aspect isthe stability of the stabilizer itself prior to application as astabilizer, e.g. its storage stability and ease of handling as amaterial. Regarding phosphorus-based stabilizers, the stability of thestabilizer itself against humid conditions prior to its addition to thematerial to be stabilized is often an issue. For example, hydrolyticstability is an important factor for polymer production facilities. In ahot and humid environment, which is relatively common for polymerproduction facilities around the world (Gulf Coast of the USA;Singapore; Middle East; etc.), it is important to have a hydrolyticallystable stabilizer, not only for the stabilization activity to beexpected, but also to keep the product as a free-flowing powder orgranule. It is well known in the industry that hydrolyzed phosphites arenotoriously hard to handle and some of them even turn into a hydroscopicmaterial. The hydrolyzed material can also be corrosive to the meltprocessing equipment for polymers due to the acidic by-productsassociated with phosphite hydrolysis. For some phosphite stabilizers,the use of a hydrolysis inhibitor such as triisopropanolamine between0.5-1% by weight is often commercially applied. A phosphorous-basedstabilizer, which shows a relative stability against hydrolysis underhumid conditions is therefore of interest. Often, the hydrolysis causesan originally free-flowing material to become sticky and thus affectnegatively the ability to add the stabilizer to the organic material tobe stabilized in an industrial environment. Independently of storagestability and ease of handling as a material, a phosphorous-basedstabilizer, which keeps despite of exposure to humid conditions itsstabilization activity or at least does not lose to the same extent ascompared to a related phosphorous-based stabilizer its stabilizationactivity, is also of interest. Furthermore, a hydrolysed stabilizer cannegatively affect the organic material to be stabilized with blackspecks due to the acidic nature (phosphorus based acids) of thehydrolysed stabilizer.

It has now been found that a specific group of benzofuran-2-onediphosphate derivatives is suitable for stabilization of an organicmaterial against degradation by heat, light and/or oxidation.

The present invention relates to a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation, andb) a compound of formula I-P, I-O or I-M

wherein

-   -   R^(1P) represents one of the subformulae II-P, II-O or II-M

-   -   R^(1O) represents one of the subformulae II-O or II-M, or    -   R^(1M) represents the subformula II-M;        R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen or        C₁-C₈-alkyl,        R^(P2), R^(P3), R^(P5) and R^(P6) are independently from each        other hydrogen or C₁-C₈-alkyl,        R^(O1), R^(O2), R^(O5) and R^(O6) are independently from each        other hydrogen or C₁-C₈-alkyl, and        R^(M1), R^(M3), R^(M5) and R^(M6) are independently from each        other hydrogen or C₁-C₈-alkyl.

A compound of formula I-P, I-O or I-M possess at least one asymmetriccarbon atom, i.e. a carbon atom at the 3-position of thebenzofuran-2-one structural unit. Further asymmetric carbon atoms can bepresent in alkyl substituents with at least four carbon atoms. Aphosphorus atom, which is substituted with four different substituents,is an asymmetric phosphorus atom. The invention relates to the resultingenantiomers, resulting diastereomers or mixtures thereof.

C₁-C₈-alkyl is linear or branched and for example methyl, ethyl,n-propyl, 1-methyl-ethyl, n-butyl, 1-methyl-propyl, 2-methyl-propyl,1,1-dimethyl-ethyl, n-pentyl, 1-methyl-butyl, 3-methyl-butyl, n-hexyl,1-methyl-pentyl, 2-methyl-pentyl, 4-methyl-pentyl, 2-ethyl-butyl,n-heptyl, 1-methyl-hexyl, n-octyl, 1-methyl-heptyl, 2-ethyl-hexyl,5,5-dimethyl-hexyl or 1,1,3,3-tetramethyl-butyl. Preferred isC₁-C₄-alkyl or C₈-alkyl, particularly methyl, ethyl, 1-methyl-ethyl,1-methyl-propyl 1,1-dimethylethyl or 1,1,3,3-tetramethyl-butyl.Preferred is C₁-C₄-alkyl, particularly methyl, ethyl, 1-methylethyl,1-methyl-propyl 1,1-dimethyl-ethyl and very particular methyl,1-methyl-propyl or 1,1-dimethyl-ethyl.

An organic material susceptible to oxidative, thermal or light-induceddegradation is for example a polymer, an oligohydroxy compound, a wax, afat or a mineral oil.

A polymer can be natural, semi-synthetic or synthetic. A natural polymeris isolated from a natural source without further syntheticmodifications. A synthetic polymer does not contain a polymer partisolated from a natural source. A semi-synthetic polymer contains atleast one natural polymer part, wherein the natural polymer part can besynthetically modified and/or reacted with monomers to form thesemi-synthetic polymer.

A polymer can be thermoplastic, i.e. it can be shaped into a new form atan elevated temperature, for example at a temperature in the range from135° C. to 350° C., especially from 150° C. to 340° C.

A copolymer is a polymer, wherein at least two different monomers areco-polymerized. Preferred are copolymers, wherein the weight content ofone monomer is above 50% based on the weight of all monomers.

Preferably, a polymer is a substance consisting of moleculescharacterized by the sequence of one or more types of monomer units andcomprising a simple weight majority of molecules containing at leastthree monomer units which are covalently bound to at least one othermonomer unit or other reactant and consists of less than a simple weightmajority of molecules of the same molecular weight. Such molecules mustbe distributed over a range of molecular weights wherein differences inthe molecular weight are primarily attributable to differences in thenumber of monomer units. In the context of this definition a monomerunit means the reacted form of a monomer in a polymer.

Examples of a polymer are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups 4, 5, 6 (for        example chromium) or 7 of the Periodic Table. These metals        usually have one or more than one ligand, typically oxides,        halides, alcoholates, esters, ethers, amines, alkyls, alkenyls        and/or aryls that may be either π- or σ-coordinated. These metal        complexes may be in the free form or fixed on substrates,        typically on activated magnesium chloride, titanium(III)        chloride, alumina or silicon oxide. These catalysts may be        soluble or insoluble in the polymerisation medium. The catalysts        can be used by themselves in the polymerisation or further        activators may be used, typically metal alkyls, metal hydrides,        metal alkyl halides, metal alkyl oxides or metal alkyloxanes,        said metals being elements of groups 1, 2 and/or 3 of the        Periodic Table. The activators may be modified conveniently with        further ester, ether, amine or silyl ether groups. These        catalyst systems are usually termed Phillips, Standard Oil        Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single        site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is generated in-situ; propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and their salts (ionomers) as well as terpolymers of ethylenewith propylene and a diene such as hexadiene, dicyclopentadiene orethylidene-norbornene; and mixtures of such copolymers with one anotherand with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA),LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbonmonoxide copolymers and mixtures thereof with other polymers, forexample polyamides.

A special copolymer of two monoolefins is a pipe grade polypropylenerandom copolymer, which is obtainable from the polymerization of morethan 90% by weight of propylene and of less than 10% by weight,typically between 2 and 6% by weight, of ethylene.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications there-of (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereisotactic polymers are preferred. Stereoblock polymers are alsoincluded.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyl-toluene, all isomers of ethyl styrene,propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene,and mixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes, for example polyurethanes synthesized from a polyoland an aliphatic or aromatic polyisocyanate such as polyurethanesderived from hydroxyl-terminated polyethers, polyesters orpolybutadienes on the one hand and aliphatic or aromatic polyisocyanateson the other, as well as precursors thereof.

Hydroxyl-terminated polyethers are known and are prepared, for example,by polymerizing epoxides such as ethylene oxide, propylene oxide,butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin withthemselves, for example in the presence of BF₃, or by addition reactionof these epoxides, alone or as a mixture or in succession, with startingcomponents containing reactive hydrogen atoms, such as water, alcohols,ammonia or amines, for example ethylene glycol, propylene 1,3- and1,2-glycol, trimethylolpropane, 4,4′-dihydroxydiphenylpropane, aniline,ethanolamine or ethylenediamine. Sucrose polyethers are also suitable inaccordance with the invention. In many cases preference is given tothose polyethers which predominantly (up to 90% by weight, based on allthe OH groups present in the polyether) contain primary OH groups.Furthermore, polyethers modified by vinyl polymers, as are formed, forexample, by polymerizing styrene and acrylonitrile in the presence ofpolyethers, are suitable, as are polybutadienes containing OH groups.

Particularly, a polyol compound has a molecular weight of 400-10000,especially 800 to 10000, and is a compound containing more than one OHgroup, especially containing from 2 to 8 OH groups, especially from 2 to4.

Suitable polyisocyanates are aliphatic or aromatic, for example ethylenediisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylenediisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate,cyclohexane 1,3- and -1,4-diisocyanate and also any desired mixtures ofthese isomers,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and2,6-hexahydrotolylene diisocyanate and also any desired mixtures ofthese isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate,perhydro-2,4′- and/or -4,4′-diphenylmethanediisocyanate, 1,3- and1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, and alsoany desired mixtures of these isomers, diphenylmethane 2,4′- and/or-4,4′-diisocyanate, naphthylene 1,5-diisocyanate, triphenylmethane4,4′,4″-triisocyanate, polyphenyl-polymethylene polyisocyanates as areobtained by aniline-formaldehyde condensation followed byphosgenization, m- and p-isocyanatophenylsulfonyl isocyanates,perchlorinated aryl polyisocyanates, polyisocyanates containingcarbodiimide groups, polyisocyanates containing allophanate groups,polyisocyanates containing isocyanurate groups, polyisocyanatescontaining urethane groups, polyisocyanates containing acylated ureagroups, polyisocyanates containing biuret groups, polyisocyanatescontaining ester groups, reaction products of the abovementionedisocyanates with acetals, and polyisocyanates containing polymeric fattyacid radicals.

It is also possible to employ the isocyanate group-containingdistillation residues, as they are or dissolved in one or more of theabovementioned polyisocyanates, which are obtained in the course of theindustrial preparation of isocyanates. It is additionally possible touse any desired mixtures of the abovementioned polyisocyanates.

Preferred are 2,4- or 2,6-tolylene diisocyanate and any desired mixturesof these isomers (“TDI”), polyphenyl-polymethylene-polyisocyanates asprepared by aniline-formaldehyde condensation followed by phosgenization(“crude MDI”) or polyisocyanates containing carbodiimide, urethane,allophanate, isocyanurate, urea or biuret groups (“modifiedpolyisocyanates”).

The polyurethanes can be homogeneous polyurethanes or cellular.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimides,polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones or lactides, forexample polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalateand polyhydroxybenzoates as well as copolyether esters derived fromhydroxyl-terminated polyethers, and also polyesters modified withpolycarbonates or MBS. Copolyesters may comprise, for example—but arenot limited to—polybutylenesuccinate/terephthalate,polybutyleneadipate/terephthalate,polytetramethyleneadipate/terephthalate, polybutylenesuccinate/adipate,polybutylenesuccinate/carbonate, poly-3-hydroxybutyrate/octanoatecopolymer, poly-3-hydroxybutyrate/hexanoate/decanoate terpolymer.Furthermore, aliphatic polyesters may comprise, for example—but are notlimited to—the class of poly(hydroxyalkanoates), particularly,poly(propiolactone), poly(butyrolactone), poly(pivalolactone),poly(valerolactone) and poly(caprolactone), polyethylenesuccinate,polypropylenesuccinate, polybutylenesuccinate,polyhexamethylenesuccinate, polyethyleneadipate, polypropyleneadipate,polybutyleneadipate, polyhexamethyleneadipate, polyethyleneoxalate,polypropyleneoxalate, polybutyleneoxalate, polyhexamethyleneoxalate,polyethylenesebacate, polypropylenesebacate, polybutylenesebacate andpolylactic acid (PLA) as well as corresponding polyesters modified withpolycarbonates or MBS. The term “polylactic acid (PLA)” designates ahomo-polymer of preferably poly-L-lactide and any of its blends oralloys with other polymers; a co-polymer of lactic acid or lactide withother monomers, such as hydroxycarboxylic acids, like for exampleglycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid,4-hydroxy-valeric acid, 5-hydroxy-valeric acid, 6-hydroxy-caproic acidand cyclic forms thereof; the terms “lactic acid” or “lactide” includeL-lactic acid, D-lactic acid, mixtures and dimers thereof, i.e.L-lactide, D-lactide, meso-lactide and any mixtures thereof.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

23. Drying and non-drying alkyd resins.

24. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

25. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

26. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyan urates,polyisocyanates or epoxy resins.

27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

28. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

29. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

An oligohydroxy compound possesses two or more hydroxy groups, but isnot a polymer according to the definition for polymers of theOrganization for Economic Co-operation and Development. Examples foroligohydroxy compounds are ethylene glycol, propylene glycol,butane-1,2-diol, butane-1,4-diol, hexane-1,2-diol, hexane-1,6-diol,cyclohexane-1,2-diol, glycerol, pentaerythritol, D-fructose, D-glucitol,mannitol or saccharose.

A wax is for example an ester of wax acids with alcohols, for exampleC₂₂-C₃₄-monocarboxylic acids esterified with C₁₅-C₃₆-monoalcohols,triterpene alcohols orsteriod alcohol. Such esters are for examplecontained in carnauba wax, beeswax or jojoba oil. A further type of waxis for example a Fischer-Tropsch-wax, which is based on C₁-chemistry.

A fat is an ester of glycerol and an aliphatic saturated or unsaturatedcarboxylic acid, for example a monoacyl glycerol, a diacyl glycerol or atriacyl glycerol. Preferably, the carboxylic acid is linear. A mineraloil is an aliphatic liquid saturated hydrocarbon, which is obtained bydistillation from crude oil, coal tar, bituminous tar, wood or peat. Themineral oil can be liquid, semi-solid or solid. In the latter case, itis called mineral fat. Examples for mineral oils are benzine, dieseloil, fuel oil, bitumen or kerosine. Preferred mineral oils are saturatedC₈-C₂₂-hydrocarbons, which are linear or branched. Especially preferredare saturated C₈-C₁₄-hydrocarbons.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation, wherein the organic material is a polymer, anoligohydroxy compound, a wax, a fat or a mineral oil, andb) a compound of formula I-P, I-O or I-M.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation, wherein the organic material is a polymer,particularly a synthetic or semisynthetic polymer and very particular asynthetic or semisynthetic thermoplastic polymer, andb) a compound of formula I-P, I-O or I-M.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation, wherein the organic material is a polymer,which is a polyolefin or a copolymer thereof, a polystyrene or acopolymer thereof, a polyurethane or a copolymer thereof, a polyether,which is obtainable by the polymerization of an epoxide, an oxetane or atetrahydrofuran, or a copolymer thereof, a polyester or a copolymerthereof, a polycarbonate or a copolymer thereof, a poly(vinyl chloride)or a copolymer thereof, a poly(vinylidene chloride) or a copolymerthereof, a polysulfone or a copolymer thereof, a poly(vinyl acetate) ora copolymer thereof, a poly(vinyl alcohol) or a copolymer thereof, apoly(vinyl acetal) or a copolymer thereof, or a polyamide or a copolymerthereof, andb) a compound of formula I-P, I-O or I-M.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation, wherein the organic material is a polyolefinor a copolymer thereof, a polystyrene or a copolymer thereof, or apolyurethane or a copolymer thereof, particularly wherein the organicmaterial is a polyolefin or a copolymer thereof, or a polystyrene or acopolymer thereof, andb) a compound of formula I-P, I-O or I-M.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation, wherein the organic material is a polyolefinor a copolymer thereof, andb) a compound of formula I-P, I-O or I-M.

Preferences for a compound of formula I-P, I-O or I-M in theaforementioned compositions are as following:

Preferred is a compound of formula I-P, I-O or I-M, wherein

R⁴ and R⁶ are hydrogen, andR⁵ and R⁷ are independently from each other hydrogen or C₁-C₈-alkyl,particularly hydrogen or C₁-C₄-alkyl.

Preferred is a compound of formula I-P, I-O or I-M, wherein

R⁴, R⁶ and R⁷ are hydrogen and R⁵ is hydrogen or C₁-C₈-alkyl,particularly hydrogen or C₁-C₄-alkyl.

Preferred is a compound of formula I-P, I-O or I-M, wherein

R^(P2) and R^(P6) are independently from each other hydrogen orC₁-alkyl, R^(P3) and R^(P5) are independently from each other hydrogenor C₁-C₄-alkyl,R^(O1) and R^(O6) are independently from each other hydrogen orC₁-C₈-alkyl, R^(O2) is hydrogen or C₁-alkyl and R^(O5) is hydrogen orC₁-C₄-alkyl,R^(M1) is hydrogen or C₁-alkyl, R^(M3) and R^(M5) are independently fromeach other hydrogen or C₁-C₄-alkyl, and R^(M6) is hydrogen orC₁-C₈-alkyl.

Preferred is a compound of formula I-P, I-O or I-M, wherein

R^(P2) and R^(P6) are hydrogen and R^(P3) and R^(P5) are independentlyfrom each other hydrogen or C₁-C₄-alkyl,R^(O1) is hydrogen or C₁-C₈-alkyl, R^(O2) is hydrogen, R^(O5) and R^(O6)are independently from each other hydrogen or C₁-C₄-alkyl,R^(M1) and R^(M3) are hydrogen or C₁-alkyl, R^(M5) is hydrogen orC₁-C₄-alkyl, and R^(M6) is hydrogen or C₁-C₈-alkyl.

Preferred is a compound of formula I-P, I-O or I-M, wherein

R^(P2) and R^(P6) are hydrogen and R^(P3) and R^(P5) are independentlyfrom each other hydrogen or C₁-C₄-alkyl, wherein one of R^(P3) andR^(P5) is not C₄-alkyl,R^(O1) is hydrogen or C₁-C₈-alkyl, R^(O2) is hydrogen, R^(O5) ishydrogen or C₁-C₃-alkyl, and R^(O6) is hydrogen or C₁-C₄-alkyl, andR^(M1) and R^(M3) are hydrogen or C₁-alkyl, R^(M5) is hydrogen orC₁-C₃-alkyl, and R^(M6) is hydrogen or C₁-C₈-alkyl.

Preferred is a compound of formula I-P, I-O or I-M, wherein

R^(P2) and R^(P6) are hydrogen and one of R^(P3) and R^(P5) is hydrogen,whereas the other one is hydrogen or C₁-C₄-alkyl,R^(O1) is hydrogen or C₁-C₈-alkyl, R^(O2) is hydrogen, R^(O5) ishydrogen or C₁-alkyl, and R^(O6) is hydrogen or C₁-C₄-alkyl, andR^(M1), R^(M3) and R^(M5) are hydrogen, and R^(M6) is hydrogen orC₁-C₈-alkyl.

Preferred is a compound of formula I-P, I-O or I-M, wherein

R^(1P) represents the subformula II-P,R^(1O) represents the formula II-O, andR^(1M) represents the subformula II-M.

Preferred is a compound of formula I-P, I-O or I-M, which is of formulaI-P or I-O, and wherein

R^(1P) or R^(1O) does not represent the subformula II-M.

Preferred is a compound of formula I-P, I-O or I-M, which is of formulaI-P or I-O, wherein

R^(1P) represents one of the subformulae II-P or II-O,R^(1O) represents the subformula II-O.

Preferred is a compound of formula I-P, I-O or I-M, which is of formulaI-P, wherein

R^(1P) represents the subformula II-P.

Preferred is a compound of formula I-P, I-O or I-M, which is of formulaI-O, wherein

R^(1O) represents the subformula II-O.

The above cited preferences for a compound of formula I-P, I-O or I-Mrefer individually to three structural units of formula I-P, I-O or I-M.These structural units comprise the benzofuran-2-one unit including R⁴,R⁵, R⁶ and R⁷, the linking phenylene unit including R^(P2), R^(P3),R^(P5), R^(P6), R^(O1), R^(O2), R^(O5), R^(O6), R^(M1), R^(M3), R^(M5),and R^(M6), and the other-close-to-phosphorus atom unit includingR^(1P), R^(1O) and R^(1M). The above cited preferences for the threestructural units can be combined. Examples thereof are provided below.

Preferred is a compound of formula I-P, I-O or I-M, wherein

R^(1P) represents one of the subformulae II-P, II-O or II-M,R^(1O) represents one of the subformulae II-O or II-M,R^(1M) represents the subformula II-M,R⁴ and R⁶ are hydrogen,R⁵ and R⁷ are independently from each other hydrogen or C₁-C₈-alkyl,R^(P2) and R^(P6) are independently from each other hydrogen orC₁-alkyl,R^(P3) and R^(P5) are independently from each other hydrogen orC₁-C₄-alkyl,R^(O1) and R^(O6) are independently from each other hydrogen orC₁-C₈-alkyl,R^(O2) is hydrogen or C₁-alkyl,R^(O5) is hydrogen or C₁-C₄-alkyl,R^(M1) is hydrogen or C₁-alkyl,R^(M3) and R^(M5) are independently from each other hydrogen orC₁-C₄-alkyl, andR^(M6) is hydrogen or C₁-C₈-alkyl.

Preferred is a compound of formula I-P, I-O or I-M, wherein

R^(1P) represents the subformula II-P,R^(1O) represents the subformulae II-O,R^(1M) represents the subformula II-M,R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen orC₁-C₈-alkyl,R^(P2), R^(P3), R^(P5) and R^(P6) are independently from each otherhydrogen or C₁-C₈-alkyl,R^(O1), R^(O2), R^(O5) and R^(O6) are independently from each otherhydrogen or C₁-C₈-alkyl, andR^(M1), R^(M3), R^(M5) and R^(M6) are independently from each otherhydrogen or C₁-C₈-alkyl,

Preferred is a compound of formula I-P, I-O or I-M, which is of formulaI-P or I-O, wherein

R^(1P) represents one of the subformulae II-P or II-O,R^(1O) represents the subformula II-O,R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen orC₁-C₈-alkyl,R^(P2), R^(P3), R^(P5) and R^(P6) are independently from each otherhydrogen or C₁-C₈-alkyl, andR^(O1), R^(O2), R^(O5) and R^(O6) are independently from each otherhydrogen or C₁-C₈-alkyl.

Preferred is a compound of formula I-P, I-O or I-M, which is of formulaI-P or I-O, wherein

R^(1P) represents one of the subformulae II-P or II-O,R^(1O) represents the subformula II-O,R⁴ and R⁶ are hydrogen,R⁵ and R⁷ are independently from each other hydrogen or C₁-C₈-alkyl,R^(P2) and R^(P6) are hydrogen,R^(P3) and R^(P5) are independently from each other hydrogen orC₁-C₄-alkyl, wherein one of R^(P3) andR^(P5) is not C₄-alkyl,R^(O1) is hydrogen or C₁-C₈-alkyl,R^(O2) is hydrogen,R^(O5) is hydrogen or C₁-C₃-alkyl, andR^(O6) is hydrogen or C₁-C₄-alkyl.

Preferred is a compound of formula I-P, which is compound (403), or acompound of formula I-O, which is compound (402). The structure ofcompound (403) is depicted in the synthetic examples S-4a or S-4b, andthe structure of compound (402) is depicted in the synthetic examplesS-3a, S3b or S-3c.

The employed amount of component b), i.e. a compound of formula I-P, I-Oor I-M, in regard to component a), i.e. an organic material susceptibleto oxidative, thermal or light-induced degradation, varies with theparticular organic material susceptible to oxidative, thermal orlight-induced degradation and the desired degree of protection.

Preferred is a composition, which comprises an organic materialsusceptible to oxidative, thermal or light-induced degradation ascomponent a) and a compound of formula I-P, I-O or I-M as component b),wherein component b) is contained in an amount of 0.0005% to 10%,particularly from 0.001 to 2%, especially from 0.0025 to 1% and veryespecially from 0.005 to 0.5%, based on the weight of component a).

Optionally, a composition comprising an organic material as component a)and a compound of formula I-P, I-O or I-M as component b) contains afurther additive as component c).

A further additive can be selected from the following list:

1. Antioxidants

1.1. Alkylated monophenols, which do not contain a phosphite group or abenzofuran-2-one group, for example 2,6-di-tert-butyl-4-methylphenol,2-tert-butyl-4,6-dimethylphenol, 2,6-di-tertbutyl-4-ethylphenol,2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-40methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyl-1′-tetradecyl-methyl)-phenol and mixturesthereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,8-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tertbutyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, for example with methanol, ethanol,n-octanol, i-octanol, a mixture of linear and branched C₇-C₉-alkanol,octadecanol, a mixture of linear and branched C₁₃-C₁₅-alkanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxylethyl)isocyanurate,N,N′-bis-(hydroxylethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, for example with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, for example with methanol, ethanol,octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, for example with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, forexampleN,N′-bis(3,5-ditert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard XL-1®, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

2.1.2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tertbutyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-O2H-benzotriazole with polyethylene glycol 300;

where R′=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-β-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate,N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline and neopentyltetra(α-cyano-β,β-diphenylacrylate).

2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitriletriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-ditert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl)succinate,bis-[2,2,6,6-tetramethyl-1-(undecyloxy)-piperidin-4-yl] carbonate,linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropyl-amino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268 64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxy-piperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine, a mixture of oligomericcompounds which are the formal condensation products ofN,N′-bis-(2,2,6,6-tetramethyl-1-propoxy-piperidin-4-yl)-hexane-1,6-diamineand2,4-dichloro-6-{n-butyl-(2,2,6,6-tetramethyl-1-propoxy-piperidin-4-yl)-amino}-[1,3,5]triazineend-capped with 2-chloro-4,6-bis-(di-n-butylamino)-[1,3,5]triazine, amixture of oligomeric compounds which are the formal condensationproducts ofN,N′-bis-(2,2,6,6-tetramethyl-piperidin-4-yl)-hexane-1,6-diamine and2,4-dichloro-6-{n-butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)-amino}-[1,3,5]triazineend-capped with 2-chloro-4,6-bis-(di-n-butylamino)-[1,3,5]triazine,2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor(Clariant; CAS Reg. No. 106917-31 1],5-(2-ethylhexanoyl)-oxymethyl-3,3,5-trimethyl-2-morpholinone, thereaction product of2,4-bis-[(1-cyclo-hexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis-(3-amino-propyl)ethylenediamine),1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethyl-piperazine-3-one-4-yl)amino)-s-triazine,1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazine-3-one-4-yl)amino)-s-triazine.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis¬(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, C₁₂-C₁₈ alkyl bis[4-(1-methyl-1-phenylethyl)phenyl]phosphite, C₁₂-C₁₈ alkenyl bis[4-(1-methyl-1-phenyl-ethyl)phenyl]phosphite, bis[4-(1-methyl-1-phenyl-ethyl)phenyl] [(E)-octadec-9-enyl]phosphite, decyl bis[4-(1-methyl-1-phenylethyl)phenyl] phosphite,didecyl [4-(1-methyl-1-phenyl-ethyl)phenyl] phosphite,[4-(1-methyl-1-phenyl-ethyl)phenyl] bis[(E)-octadec-9-enyl] phosphite,trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritoldiphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite,[2-tert-butyl-4-[1-[5-tert-butyl-4-di(tridecoxy)phosphanyloxy-2-methyl-phenyl]butyl]-5-methyl-phenyl]ditridecyl phosphite, tristearyl sorbitol triphosphite, a mixture of atleast two different tris(mono-C₁-C₈-alkyl)phenyl phosphites such as forexample mentioned in U.S. Pat. No. 7,468,410 B2 as products of examples1 and 2, a mixture of phosphites comprising at least two differenttris(amylphenyl) phosphites such as for example mentioned in U.S. Pat.No. 8,008,383 B2 as mixtures 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24,25 and 26, a mixture of a least four different phosphites comprisingtris[4-(1,1-dimethylpropyl)phenyl] phosphite,[2,4-bis(1,1-dimethylpropyl)phenyl] bis[4-(1,1-dimethylpropyl)phenyl]phosphite, bis[2,4-bis(1,1-dimethylpropyl)phenyl][4-(1,1-dimethylpropyl)phenyl]phosphite andtris[2,4-bis(1,1-dimethylpropyl)phenyl] phosphite, a mixture ofphosphites comprising at least two different tris(butylphenyl)phosphites such as for example mentioned in U.S. Pat. No. 8,008,383 B2as mixtures 34, 35, 36, 37, 38, 39 and 40, an oxyalkylene-bridgedbis-(di-C₆-aryl) diphosphite or an oligomeric phosphite obtainable bycondensation under removal of hydrogen chloride of (i) atrichlorophosphane, with (ii) a dihydroxyalkane interrupted by one ormore oxygen atoms and with (iii) a mono-hydroxy-C₆-arene such as forexample mentioned in U.S. Pat. No. 8,304,477 B2 as products of examples1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17, apolymeric phosphite obtainable by transesterification under removal ofphenol of (i) triphenyl phosphite with (ii) a dihydroxyalkane optionallyinterrupted by one or more oxygen atoms and/or abis(hydroxyalkyl)(alkyl)amine and with (iii) a mono-hydroxyalkaneoptionally interrupted by one or more oxygen atoms such as for examplementioned in U.S. Pat. No. 8,563,637 B2 as products of examples 1, 2, 3,4, 5, 6, 7, 8, 9, 10 and 11, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocine,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocine,1,3,7,9-tetra-tert-butyl-11-octoxy-5H-benzo[d][1,3,2]benzodioxaphosphocine,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetratert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane,2-tert-butyl-6-methyl-4-[3-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropyl]phenol,phosphites of formulae PRE-I-P, PRE-I-O or PRE-I-M such as for examplecompounds (102) and (103) [formulae PRE-I-P, PRE-I-O or PRE-I-M depictedfurther below as starting materials for the further embodiment of aprocess for manufacturing a compound of formula I-P, I-O or I-M, statedcompounds (102) and (103) are depicted in the experimental part asproducts of examples S-1 and S-2],

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168, RTM BASF),tris(nonylphenyl) phosphite,

5. Hydroxylamines and amine N-oxides, for exampleN,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine,N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecylnitrone,N-octadecyl-alpha-heptadecylnitrone,N-hexadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-heptadecylnitrone, Noctadecyl-alpha-hexadecylnitrone,nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenatedtallow amine.

7. Amine N-oxides, for example N,N-bis-(hydrogenated rape-oilalkyl)-N-methyl-amine N-oxide, N-hexydecyl-N-methyl-N-octadecyl-1-amineoxide, N-hexydecyl-N-methyl-N-hexadecyl-1-amine oxide,N-octadecyl-N-methyl-N-octadecyl-1-amine oxide.

8. Thiosynergists, for example dilauryl thiodipropionate, dimistrylthiodipropionate, distearyl thiodipropionate or pentaerythritoltetrakis-[3-(n-lauryl)-propionic acid ester],

9. Peroxide scavengers, for example esters of α-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

10. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorous compounds and salts of divalent manganese.

11. Acid scavengers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate and zincpyrocatecholate.

12. Benzofuranones and indolinones, which are different to a compound offormula I-P, I-O and I-M and different to a compound of formulaePRE-I-P, PRE-I-O and PRE-I-M, for example those disclosed in U.S. Pat.Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643;DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-ditert-butylbenzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2-acetoxy-4-(1,1,3,3-tetramethyl-butyl)-phenyl)-5-(1,1,3,3-tetramethyl-butyl)-benzofuran-2-one,[5-tert-butyl-2-(5-tert-butyl-2-oxo-3H-benzofuran-3-yl)phenyl]3,5-ditert-butyl-4-hydroxy-benzoate,[6-[6-[2-[4-(5,7-ditert-butyl-2-oxo-3H-benzofuran-3-yl)phenoxy]ethoxy]-6-oxo-hexoxy]-6-oxo-hexyl]6-hydroxyhexanoate.

13. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers), IrgaclearXT 386 (RTM BASF),1,3:2,4-bis(3′,4′-dimethylbenzylidene)-sorbitol,1,3:2,4-di(paramethyldibenzylidene)-sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

14. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass beads, asbestos, talc, kaolin, bentonite,mica, hydrotalcite, barium sulfate, metal oxides and hydroxides, carbonblack, graphite, wood flour and flours or fibers of other naturalproducts, synthetic fibers.

15. Other additives, for example plasticisers, lubricants, rheologyadditives, catalysts, flow-control agents, optical brighteners,flameproofing agents, antistatic agents and blowing agents.

It has also been surprisingly found that many compounds of formula I-P,I-O or I-M, in combination with a further additive are very effectivefor stabilization of an organic material against degradation by heat,light and/or oxidation, particularly in combination with a phenolicantioxidant or a phosphite or phosphonite, which is different to acompound of formula I-P, I-O or I-M, as a further additive. It oftenturns out that the presence of compounds of formula I-P, I-O or I-Mallows to reduce the amount of the further additive in excess of a mere1 to 1 substitution based on weight of the further additive.

Preferred is a composition, which comprises an organic materialsusceptible to oxidative, thermal or light-induced degradation ascomponent a), a compound of formula I-P, I-O or I-M as component b) anda further additive as component c).

Preferred is a composition, wherein the weight ratio of component b) tocomponent c) is from 10:1 to 1:30, particularly from 4:1 to 1:20,especially from 2:1 to 1:10.

Preferred is a composition, wherein the weight ratio of component b) tocomponent c) is from 10:1 to 1:30, particularly from 4:1 to 1:20,especially from 2:1 to 1:10, and wherein the overall amount of componentb) and component c) is below 80%, especially 50%, by weight of componenta).

Preferred is a composition, wherein the weight ratio of component b) tocomponent c) is from 4:1 to 1:20, particularly from 2:1 to 1:10, and theoverall amount of component b) and component c) is between 0.005% and50% based on the weight of component a), particularly between 0.005% and10% and very particular between 0.005% and 1%.

Preferred is a composition, which comprises as component c) a furtheradditive, which is an antioxidant, an UV absorber, a hindered aminelight stabilizer, a nickel compound, a metal deactivator, a phosphite orphosphonite, which is different to a compound of formula I-P, I-O orI-M, a hydroxylamine or amine N-oxide, a thiosynergist, a peroxidescavenger, a nucleating agent, a filler or reinforcing agent.

Preferred is a composition, which comprises as component c) a furtheradditive, which is a phosphite or phosphonite, which is different to acompound of formula I-P, I-O or I-M, an acid scavenger, a phenolicantioxidant or an aminic antioxidant.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation,b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is a phenolic antioxidant or a phosphite orphosphonite, which is different to a compound of formula I-P, I-O orI-M.

Preferred is a composition, which comprises as component c) a phenolicantioxidant.

Preferred is a composition, which comprises as component c) a phenolicantioxidant, which is an ester ofβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid.

A phenolic antioxidant of special relevance is a compound as depicted

and for which one chemical name istetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]methaneor alternativelytetrakis-[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionyloxymethyl]methane.It is contained in the commercial product Irganox 1010 (RTM BASF).

Another phenolic antioxidant of special relevance is a compound asdepicted

and for which one chemical name is stearylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate or alternativelystearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate. It iscontained in the commercial product Irganox 1076 (RTM BASF).

Preferred is a composition, which comprises as component c) a phenolicantioxidant, which istetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]methaneor stearyl β-(3,5-ditert-butyl-4-hydroxyphenyl)-propionate.

Preferred is a composition, which comprises as component c) a phosphiteor phosphonite, which is different to a compound of formula I-P, I-O orI-M.

A phosphite of special relevance is a compound as depicted

and for which one chemical name is tris-(2,4-di-tert-butylphenyl)phosphite. It is contained in the commercial product Irgafos 168 (RTMBASF).

Preferred is a composition, which comprises as component c) a phosphite,which is tris-(2,4-ditert-butylphenyl) phosphite.

A phosphite of special relevance is of formulae PRE-I-P, PRE-I-O orPRE-I-M.

Preferred is a composition, which comprises as component b) a compoundof formula I-P, I-O or I-M, and as component c) a further additive,which is a phosphite of formula PRE-I-P, PRE-I-O or PRE-I-M.

Preferred is a composition, which comprises as component b) a compoundof formula I-P, I-O or I-M, and as component c) a further additive,which is a phosphite of formula PRE-I-P, PRE-I-O or PRE-I-M, wherein

when component b) is of formula I-P, the phosphite is of formulaPRE-I-P,wherein the respective substituents at formula I-P and at formulaPRE-I-P are the same,when component b) is of formula I-O, the phosphite is of formulaPRE-I-O,wherein the respective substituents at formula I-O and at formulaPRE-I-O are the same,when component b) is of formula I-M, the phosphite is of formulaPRE-I-M,wherein the respective substituents at formula I-M and at formulaPRE-I-M are the same.

An example for the aforementioned composition is a compositioncomprising as component b) compound (402) and as component c) compound(102) or a composition comprising as component b) compound (403) and ascomponent c) compound (103). The structures of compounds (102), (103),(402) and (403) are depicted at the respective examples S-1, S-2, S-3aand S-4a.

Optionally, a composition comprising an organic material susceptible tooxidative, thermal or light-induced degradation as component a), acompound of formula I-P, I-O or I-M as component b) and a furtheradditive as component c) contains a second further additive as componentd).

Preferred is a composition, which comprises an organic materialsusceptible to oxidative, thermal or light-induced degradation ascomponent a), a compound of formula I-P, I-O or I-M as component b), afurther additive as component c) and a second further additive ascomponent d).

Preferred is a composition, wherein the weight ratio of component b) tocomponent d) is from 10:1 to 1:30, particularly from 4:1 to 1:20,especially from 2:1 to 1:10.

Preferred is a composition, wherein the weight ratio of component b) tocomponent d) is from 10:1 to 1:30, particularly from 4:1 to 1:20,especially from 2:1 to 1:10, and wherein the overall amount of componentb), component c) and component d) is between 0.005% and 50% by weight ofcomponent a), particularly between 0.005% and 10% and very particularbetween 0.005% and 1%.

Preferred is a composition, which comprises a component a), a componentb), as component c) a further additive, which is selected from the groupconsisting of a phosphite or phosphonite, which is different to acompound of formula I-P, I-O or I-M, an acid scavenger, a phenolicantioxidant and an aminic antioxidant, and as component d) a secondfurther additive; with the proviso that component d) is a differentcompound than component c).

Preferred is a composition, which comprises a component a), a componentb), a component c) and a component d), wherein component c) andcomponent d) are independently from each other a phosphite orphosphonite, which is different to a compound of formula I-P, I-O orI-M, an acid scavenger, a phenolic antioxidant or an aminic antioxidant;with the proviso that component d) is a different compound thancomponent c).

Preferred is a composition, which comprises a component a), a componentb), as component c) a phenolic antioxidant and as component d) an aminicantioxidant.

Preferred is a composition, which comprises a component a), a componentb), as component c) a phenolic antioxidant and as component d) aphosphite or phosphonite, which is different to a compound of formulaI-P, I-O or I-M.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation,b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, andd) a second further additive, which is a phosphite or phosphonite, whichis different to a compound of formula I-P, I-O or I-M.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation,b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, which istetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]methaneor stearyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, andd) a second further additive, which is a phosphite or phosphonite, whichis different to a compound of formula I-P, I-O or I-M.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation,b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, andd) a second further additive, which is a phosphite of formula PRE-I-P,PRE-I-O or PRE-I-M, whereinwhen component b) is of formula I-P, the phosphite is of formulaPRE-I-P,wherein the respective substituents at formula I-P and at formulaPRE-I-P are the same,when component b) is of formula I-O, the phosphite is of formulaPRE-I-O,wherein the respective substituents at formula I-O and at formulaPRE-I-O are the same,when component b) is of formula I-M, the phosphite is of formulaPRE-I-M,wherein the respective substituents at formula I-M and at formulaPRE-I-M are the same.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation,b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, andd) a second further additive, which is a phosphite, which istris-(2,4-di-tert-butylphenyl) phosphite.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation,b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, which istetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]methaneor stearyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, andd) a second further additive, which is a phosphite of formula PRE-I-P,PRE-I-O or PRE-I-M, whereinwhen component b) is of formula I-P, the phosphite is of formulaPRE-I-P,wherein the respective substituents at formula I-P and at formulaPRE-I-P are the same,when component b) is of formula I-O, the phosphite is of formulaPRE-I-O,wherein the respective substituents at formula I-O and at formulaPRE-I-O are the same,when component b) is of formula I-M, the phosphite is of formulaPRE-I-M,wherein the respective substituents at formula I-M and at formulaPRE-I-M are the same.

Preferred is a composition, which comprises

a) an organic material susceptible to oxidative, thermal orlight-induced degradation,b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, which istetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]methaneor stearyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, andd) a second further additive, which is a phosphite, which istris-(2,4-di-tert-butylphenyl) phosphite.

A compound of formula I-P, I-O or I-M is less susceptible to hydrolysis,for example under storage of humid conditions, then is the respectiveprecursor compound of formula PRE-I-P, PRE-I-O or PRE-I-M. Accordingly,the composition comprising a component b) needs less or even nonehydrolysis inhibitor. A hydrolysis inhibitor is for exampletriisopropanol amine.

Preferred is a composition, which is free of triisopropanolamine, morepreferably fee of an aliphatic secondary or tertiary amine, which is nota hindered amine light stabilizer, most preferably free of an aliphaticsecondary or tertiary amine, very preferably free of an aliphatic amine,especially preferably free of an amine and very especially preferablyfree of a hydrolysis inhibitor.

The above described preferences for an organic material susceptible tooxidative, thermal or light-induced degradation as component a) and fora compound of formula I-P, I-O or I-M as component b) are described fora composition. These preferences apply also to the further embodimentsof the invention. At these further embodiments, the optional presence ofa further additive as component c) and the optional presence of a secondfurther additive as component d) are also included.

A further embodiment of the invention relates to a process forprotection of an organic material susceptible to oxidative, thermal orlight-induced degradation, i.e. component a), which comprises the stepsof

-   -   providing the organic material, i.e. component a), and    -   incorporating into or applying onto the provided organic        material a compound of formula I-P, I-O or I-M, i.e. component        b).

The incorporation or application of component b) can be carried out in aprocessing apparatus, particularly a heatable container equipped with astirrer, which can preferably be closed. A heatable container equippedwith a stirrer is for example a kneader, extruder, mixer or stirredvessel. Specific examples thereof are a single-screw extruder,contrarotating and corotating twin-screw extruder, planetary-gearextruder, ring extruder or co-kneader. It is also possible to use aprocessing apparatus, which contains at least one gas removalcompartment to which a vacuum can be applied and/or which can be setunder an atmosphere, wherein the oxygen content is low or oxygen isabsent, for example under a nitrogen atmosphere. Component b) can beadded directly into the processing apparatus.

Component b) can be incorporated or applied to at any stage ofprocessing of component a). If component a) is a polymer, the stage isparticularly prior to or during a shaping operation of component a) inthe processing apparatus.

Component b) can be incorporated or applied in the form of a dry powder,in a compacted form of a powder such as a granule, in the form of amelt, in encapsulated form such as encapsulation in a wax or anauxiliary polymer or in the form of a wet mixture such as a solution,dispersion or suspension for example in an inert solvent, water or oil.A dispersing or suspension agent can be present in the case of a wetmixture of component b).

Component b) can also be incorporated or applied by spraying ontocomponent a).

In case that component a) is a polymer, a further possibility forincorporation or application of component b) to component a) is additionbefore, during or directly after the polymerization of the correspondingstarting materials, e.g. monomers, of component a). For example,spraying during the deactivation of the polymerization catalysts isparticularly advantageous. If crosslinking takes place during formationof component a), incorporation or application prior to crosslinking ispreferred.

In case that component a) is a polymer, the process of incorporation orapplication is preferably a molding process, particularly aninjection-molding, blow-molding, compression-molding, roto-molding,slush-molding or extrusion-molding.

Preferred is a process, wherein the organic material susceptible tooxidative, thermal or light-induced degradation is a polymer, and whichcomprises the steps of

-   -   providing the organic material susceptible to oxidation, thermal        or light-induced degradation, and    -   incorporating of a compound of formula I-P, I-O or I-M into the        provided organic material and wherein a part or the complete        incorporation takes place at a temperature in the range from        135° C. to 350° C., preferably from 150° C. to 340° C.,        particularly from 180° C. to 330° C. and very especially from        190° C. to 320° C.

Preferred is a process, wherein component b) is incorporated or appliedto in an extruder during processing of component a), which is a polymer.

In case of a further additive and optionally a second further additive,i.e. component c) or components c) and d), component b) and the furtheradditive or the second further additive can be incorporated into orapplied onto component a) individually or mixed with one another. Ifdesired, the individual components can be mixed with one another beforeincorporation into component a) for example by dry blending, compaction,melting, encapsulation by a wax or by an auxiliary polymer or as a wetmixture in the form of a solution, a dispersion or a suspension forexample in an inert solvent, water or oil.

Component b) and a further additive and optionally a second furtheradditive can also be added to component a) in the form of a masterbatch(‘concentrate’), which contains the component b), a further additive,optionally a second further additive and a masterbatch polymer as anauxiliary polymer. The component b) and a further additive andoptionally a second further additive are incorporated into themasterbatch in a concentration of, for example, from 1% to 40% andpreferably 2% to 20% by weight of the masterbatch. The masterbatchpolymer content is the difference towards 100% by weight of themasterbatch. The masterbatch polymer must not be necessarily the samepolymer as component a) in case the latter one is a polymer.

A further embodiment of the invention relates to an article, which ismade from a composition comprising

a) an organic material susceptible to oxidative, thermal orlight-induced degradation, andb) a compound of formula I-P, I-O or I-M.

The article, which is advantageously made from a composition comprisingcomponent a), which is a polymer, and a component b), can be a shapedarticle. Examples for such a shaped article are:

I-1) Floating devices, marine applications, pontoons, buoys, plasticlumber for decks, piers, boats, kayaks, oars, and beach reinforcements.

I-2) Automotive applications, particularly bumpers, dashboards, battery,rear and front linings, moldings parts under the hood, hat shelf, trunklinings, interior linings, air bag covers, electronic moldings forfittings (lights), panes for dashboards, headlamp glass, instrumentpanel, exterior linings, upholstery, automotive lights, head lights,parking lights, rear lights, stop lights, interior and exterior trims;door panels; gas tank; glazing front side; rear windows; seat backing,exterior panels, wire insulation, profile extrusion for sealing,cladding, pillar covers, chassis parts, exhaust systems, fuelfilter/filler, fuel pumps, fuel tank, body side moldings, convertibletops, exterior mirrors, exterior trim, fasteners/fixings, front endmodule, glass, hinges, lock systems, luggage/roof racks, pressed/stampedparts, seals, side impact protection, sound deadener/insulator andsunroof.

I-3) Road traffic devices, particularly sign postings, posts for roadmarking, car accessories, warning triangles, medical cases, helmets,tires.

I-4) Devices for plane, railway, motor car (car, motorbike, trucks)including furnishings.

I-5) Devices for space applications, particularly rockets andsatellites, e.g. reentry shields.

I-6) Devices for architecture and design, mining applications, acousticquietized systems, street refuges, and shelters.

II-1) Appliances, cases and coverings in general and electric/electronicdevices (personal computer, telephone, portable phone, printer,television-sets, audio and video devices), flower pots, satellite TVbowl, and panel devices.

II-2) Jacketing for other materials such as steel or textiles.

II-3) Devices for the electronic industry, particularly insulation forplugs, especially computer plugs, cases for electric and electronicparts, printed boards, and materials for electronic data storage such aschips, check cards or credit cards.

II-4) Electric appliances, particularly washing machines, tumblers,ovens (microwave oven), dish-washers, mixers, and irons.

II-5) Covers for lights (e.g. street-lights, lamp-shades).

II-6) Applications in wire and cable (semi-conductor, insulation andcable-jacketing).

II-7) Foils for condensers, refrigerators, heating devices, airconditioners, encapsulating of electronics, semi-conductors, coffeemachines, and vacuum cleaners.

III-1) Technical articles such as cogwheel (gear), slide fittings,spacers, screws, bolts, handles, and knobs.

III-2) Rotor blades, ventilators and windmill vanes, solar devices,swimming pools, swimming pool covers, pool liners, pond liners, closets,wardrobes, dividing walls, slat walls, folding walls, roofs, shutters(e.g. roller shutters), fittings, connections between pipes, sleeves,and conveyor belts.

III-3) Sanitary articles, particularly shower cubicles, lavatory seats,covers, and sinks.

III-4) Hygienic articles, particularly diapers (babies, adultincontinence), feminine hygiene articles, shower curtains, brushes,mats, tubs, mobile toilets, tooth brushes, and bed pans.

III-5) Pipes (cross-linked or not) for water, waste water and chemicals,pipes for wire and cable protection, pipes for gas, oil and sewage,guttering, down pipes, and drainage systems.

III-6) Profiles of any geometry (window panes) and siding.

III-7) Glass substitutes, particularly extruded or co-extruded plates,glazing for buildings (monolithic, twin or multiwall), aircraft,schools, extruded sheets, window film for architectural glazing, train,transportation, sanitary articles, and greenhouse.

III-8) Plates (walls, cutting board), extrusion-coating (photographicpaper, tetrapack and pipe coating), silos, wood substitute, plasticlumber, wood composites, walls, surfaces, furniture, decorative foil,floor coverings (interior and exterior applications), flooring, duckboards, and tiles.

III-9) Intake and outlet manifolds.

III-10) Cement-, concrete-, composite-applications and covers, sidingand cladding, hand rails, banisters, kitchen work tops, roofing, roofingsheets, tiles, and tarpaulins.

IV-1) Plates (walls and cutting board), trays, artificial grass,synthetic (such as AstroTurf®), artificial covering for stadium rings(athletics), artificial floor for stadium rings (athletics), and tapes.

IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienicarticles/geotextiles/monofilaments; filters; wipes/curtains(shades)/medical applications), bulk fibers (applications such asgown/protection clothes), nets, ropes, cables, strings, cords, threads,safety seatbelts, clothes, underwear, gloves; boots; rubber boots,intimate apparel, garments, swimwear, sportswear, umbrellas (parasol,sunshade), parachutes, paraglides, sails, “balloon-silk”, campingarticles, tents, airbeds, sun beds, bulk bags, and bags. Non-wovenfabrics such as medical fabrics and related apparel, industrial apparel,outdoor fabrics, in-home furnishing and construction fabrics.

IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps,ponds, dumps, walls roofing membranes, geomembranes, swimming pools,curtains (shades)/sun-shields, awnings, canopies, wallpaper, foodpacking and wrapping (flexible and solid), medical packaging (flexible &solid), airbags/safety belts, arm- and head rests, carpets, centreconsole, dashboard, cockpits, door, overhead console module, door trim,headliners, interior lighting, interior mirrors, parcel shelf, rearluggage cover, seats, steering column, steering wheel, textiles, andtrunk trim.

V) Films (packaging, dump, laminating, agriculture and horticulture,greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, wastebags, wallpaper, stretch film, raffia, desalination film, batteries, andconnectors.

VI-1) Food packing and wrapping (flexible and solid), bottles.

VI-2) Storage systems such as boxes (crates), luggage, chest, householdboxes, pallets, shelves, tracks, screw boxes, packs, and cans.

VI-3) Cartridges, syringes, medical applications, containers for anytransportation, waste baskets and waste bins, waste bags, bins, dustbins, bin liners, wheely bins, container in general, tanks forwater/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes,crates, battery cases, troughs, medical devices such as piston,ophthalmic applications, diagnostic devices, and packing forpharmaceuticals blister.

VII-1) Extrusion coating (photo paper, tetrapack, pipe coating),household articles of any kind (e.g. appliances, thermos bottle/clotheshanger), fastening systems such as plugs, wire and cable clamps,zippers, closures, locks, and snap-closures.

VII-2) Support devices, articles for the leisure time such as sports andfitness devices, gymnastics mats, ski-boots, inline-skates, skis, bigfoot, athletic surfaces (e.g. tennis grounds); screw tops, tops andstoppers for bottles, and cans.

VII-3) Furniture in general, foamed articles (cushions, impactabsorbers), foams, sponges, dish clothes, mats, garden chairs, stadiumseats, tables, couches, toys, building kits (boards/figures/balls),playhouses, slides, and play vehicles.

VII-4) Materials for optical and magnetic data storage.

VII-5) Kitchen ware (eating, drinking, cooking, storing).

VII-6) Boxes for CD's, cassettes and video tapes; DVD electronicarticles, office supplies of any kind (ball-point pens, stamps andink-pads, mouse, shelves, tracks), bottles of any volume and content(drinks, detergents, cosmetics including perfumes), and adhesive tapes.

VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives,structural adhesives, food boxes (fruit, vegetables, meat, fish),synthetic paper, labels for bottles, couches, artificial joints (human),printing plates (flexographic), printed circuit boards, and displaytechnologies.

VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin),wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites,dolomite, silicates, glass, asbestos).

Preferred is an article, which is a shaped article, which is a film,pipe, profile, bottle, tank, container or fiber.

Preferred is a shaped article, which is molded. Particularly, themolding is effected by injection, blow, compression, roto-molding,slush-molding or extrusion.

A further embodiment to the invention relates to the use of a compoundof formula I-P, I-O or I-M, i.e. component b), for stabilizing anorganic material susceptible to oxidative, thermal or light-induceddegradation, i.e. component a), against degradation by oxidation, heator light.

Preferred is the use of component b) for stabilizing a polyurethane inthe form of a foam against scorching.

Preferred is the use of a compound of formula I-P, I-O or I-M incombination with a further additive for stabilizing an organic materialsusceptible to oxidative, thermal or light-induced degradation againstdegradation by oxidation, heat or light.

Preferred is the use of a compound of formula I-P, I-O or I-M incombination with a further additive, which is a phenolic antioxidant ora phosphite or phosphonite, which is different to a compound of formulaI-P, I-O or I-M, for stabilizing an organic material susceptible tooxidative, thermal or light-induced degradation against degradation byoxidation, heat or light.

Preferred is the use of a compound of formula I-P, I-O or I-M incombination with a further additive, which is a phenolic antioxidant,and a second further additive, which is a phosphite or phosphonite,which is different to a compound of formula I-P, I-O or I-M forstabilizing an organic material susceptible to oxidative, thermal orlight-induced degradation against degradation by oxidation, heat orlight.

Preferred is the use of a compound of formula I-P, I-O or I-M incombination with a further additive, which is a phenolic antioxidant,and a second further additive, which is a phosphite or phosphonite,which is different to a compound of formula I-P, I-O or I-M, forstabilizing an organic material susceptible to oxidative, thermal orlight-induced degradation, which is a polyolefin or a copolymer thereof,against degradation by oxidation, heat or light.

Processing of a component a) is characterized as short-term exposure ofthe component a) to heat, for example to a temperature in the range of135° C. to 350° C., particularly from 150° C. to 340° C., during thetime of processing of component a). The time of processing is short incomparison to for example the possible time of usage, for example below1 hour versus above 1 week. Usage takes typically place at atemperature, for example 0° C. to 50° C., which is below the temperatureduring processing.

Preferred is the use of component b) for stabilizing a component a)against oxidative or thermal degradation during processing.

A further embodiment of the invention relates to a compound of formulaI-P, I-O or I-M

wherein

-   -   R^(1P) represents one of the subformulae II-P, II-O or II-M

-   -   R^(1O) represents one of the subformulae II-O or II-M, or    -   R^(1M) represents the subformula II-M;        R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen or        C₁-C₈-alkyl,        R^(P2), R^(P3), R^(P5) and R^(P6) are independently from each        other hydrogen or C₁-C₈-alkyl,        R^(O1), R^(O2), R^(O5) and R^(O6) are independently from each        other hydrogen or C₁-C₈-alkyl, and        R^(M1), R^(M3), R^(M5) and R^(M6) are independently from each        other hydrogen or C₁-C₈-alkyl.

A further embodiment of the invention relates to an additivecomposition, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive selected from a group consisting of a phosphite orphosphonite, which is different to a compound of formula I-P, I-O orI-M, an acid scavenger, a phenolic antioxidant and an aminicantioxidant.

Preferred is a composition, wherein the weight ratio of component b) tocomponent c) is from 10:1 to 1:30, particularly from 4:1 to 1:20,especially from 2:1 to 1:10.

Preferred is an additive composition, wherein the weight ratio ofcomponent b) to component c) is from 10:1 to 1:30, particularly from 4:1to 1:20, especially from 2:1 to 1:10.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is a phenolic antioxidant or a phosphite orphosphonite, which is different to a compound of formula I-P, I-O orI-M.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is a phenolic antioxidant.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is a phosphite or phosphonite, which isdifferent to a compound of formula I-P, I-O or I-M.

Preferred is an additive mixture, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is a phosphite of formula PRE-I-P, PRE-I-Oor PRE-I-M.

Preferred is an additive mixture, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is a phosphite of formula PRE-I-P, PRE-I-Oor PRE-I-M, whereinwhen component b) is of formula I-P, the phosphite is of formulaPRE-I-P,wherein the respective substituents at formula I-P and at formulaPRE-I-P are the same,when component b) is of formula I-O, the phosphite is of formulaPRE-I-O,wherein the respective substituents at formula I-O and at formulaPRE-I-O are the same,when component b) is of formula I-M, the phosphite is of formulaPRE-I-M,wherein the respective substituents at formula I-M and at formulaPRE-I-M are the same.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which istetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]-methane,stearyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate ortris-(2,4-di-tert-butylphenyl) phosphite.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is tris-(2,4-di-tert-butylphenyl)phosphite.

Preferred is an additive composition, which comprises as component d) asecond further additive.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M,c) a further additive selected from a group consisting of a phosphite orphosphonite, which is different to a compound of formula I-P, I-O orI-M, an acid scavenger, a phenolic antioxidant and an aminicantioxidant, andd) a second further additive selected from a group consisting of aphosphite or phosphonite, which is different to a compound of formulaI-P, I-O or I-M, an acid scavenger, a phenolic antioxidant and an aminicantioxidant; with the proviso that component c) is a different compoundthan component d).

Preferred is a composition, wherein the weight ratio of component b) tocomponent c) is from 10:1 to 1:30, particularly from 4:1 to 1:20,especially from 2:1 to 1:10, and wherein the weight ratio of componentb) to component d) is from 10:1 to 1:30, particularly from 4:1 to 1:20,especially from 2:1 to 1:10.

Preferred is an additive composition, wherein the weight ratio ofcomponent b) to component c) is from 10:1 to 1:30, particularly from 4:1to 1:20, especially from 2:1 to 1:10, and wherein the weight ratio ofcomponent b) to component d) is from 10:1 to 1:30, particularly from 4:1to 1:20, especially from 2:1 to 1:10.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, andd) a second further additive, which is a phosphite or phosphonite, whichis different to a compound of formula I-P, I-O or I-M.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M,c) a further additive, which istetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]methaneor stearyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, andd) a second further additive, which is a phosphite or phosphonite, whichis different to a compound of formula I-P, I-O or I-M.

Preferred is an additive mixture, which comprises

b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, andd) a second further additive, which is a phosphite of formula PRE-I-P,PRE-I-O or PRE-I-M, whereinwhen component b) is of formula I-P, the phosphite is of formulaPRE-I-P,wherein the respective substituents at formula I-P and at formulaPRE-I-P are the same,when component b) is of formula I-O, the phosphite is of formulaPRE-I-O,wherein the respective substituents at formula I-O and at formulaPRE-I-O are the same,when component b) is of formula I-M, the phosphite is of formulaPRE-I-M,wherein the respective substituents at formula I-M and at formulaPRE-I-M are the same.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phenolic antioxidant, andd) a second further additive, which is tris-(2,4-di-tert-butylphenyl)phosphite.

Preferred is an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M,c) a further additive, which istetrakis-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionyloxymethyl]methaneor stearyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, andd) a second further additive, which is tris-(2,4-di-tert-butylphenyl)phosphite.

A further embodiment of this invention relates to a process formanufacturing a compound of formula I-P, I-O or I-M

wherein

-   -   R^(1P) represents one of the subformulae II-P, II-O or II-M

-   -   R^(1O) represents one of the subformulae II-O or II-M, or    -   R^(1M) represents the subformula II-M;        R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen or        C₁-C₈-alkyl,        R^(P2), R^(P3), R^(P5) and R^(P6) are independently from each        other hydrogen or C₁-C₈-alkyl,        R^(O1), R^(O2), R^(O5) and R^(O6) are independently from each        other hydrogen or C₁-C₈-alkyl, and        R^(M1), R^(M3), R^(M5) and R^(M6) are independently from each        other hydrogen or C₁-C₈-alkyl,        which comprises the step of    -   reacting a compound of formula PRE-I-P in case of formula I-P, a        compound of formula PRE-I-O in case of formula I-O or a compound        of formula PRE-I-M in case of formula I-M

with an oxidizing agent,wherein the respective substituents at formula I-P and at formulaPRE-I-P are the same, the respective substituents at formula I-O and atformula PRE-I-O are the same, and the respective substituents at formulaI-M and at formula PRE-I-M are the same.

Examples of compounds of formula PRE-I-P and PRE-I-O are described in WO2016/020322 A.

Preferably, the oxidizing agent is a compound comprising anoxygen-oxygen-single bond. Particularly, the oxidizing agent is a peroxocompound. Very particular, the oxidizing agent is a peracid, especiallyperoxyformic acid, peroxyacetic acid, peroxybenzoic acid orm-chloroperbenzoic acid (=3-chloroperoxybenzoic acid). Very especially,the oxidizing agent is m-chloroperbenzoic acid (=3-chloroperoxybenzoicacid).

Preferably, the step of reacting takes place in an aprotic solvent, forexample dichloromethane, dichloroethane or toluene.

If the amount of oxidizing agent in the process for manufacturing issubstoichiometrically chosen, an additive mixture is obtainable.

In case the amount of oxidizing agent in the process issubstoichiometrically chosen but close to stoichiometrically, then suchan additive mixture comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is a phosphite of formula MONO-I-P,MONO-I-O or MONO-I-M

wherein

-   -   R^(1P) represents one of the subformulae II-P, II-O or II-M

-   -   R^(1O) represents one of the subformulae II-O or II-M, or    -   R^(1M) represents the subformula II-M;        R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen or        C₁-C₈-alkyl,        R^(P2), R^(P3), R^(P5) and R^(P6) are independently from each        other hydrogen or C₁-C₈-alkyl,        R^(O1), R^(O2), R^(O5) and R^(O6) are independently from each        other hydrogen or C₁-C₈-alkyl, and        R^(M1), R^(M3), R^(M5) and R^(M6) are independently from each        other hydrogen or C₁-C₈-alkyl,        wherein        when component b) is of formula I-P, the phosphite is of formula        MONO-I-P,        wherein the respective substituents at formula I-P and at        formula MONO-I-P are the same,        when component b) is of formula I-O, the phosphite is of formula        MONO-I-O,        wherein the respective substituents at formula I-O and at        formula MONO-I-O are the same,        when component b) is of formula I-M, the phosphite is of formula        MONO-I-M,        wherein the respective substituents at formula I-M and at        formula MONO-I-M are the same.

In case the amount of oxidizing agent in the process for manufacturing acompound of formula I-P, I-O or I-M is substoichiometrically chosenexactly in between stoichiometrically and zero, then such an additivemixture comprises

b) a compound of formula I-P, I-O or I-M,c) a further additive, which is a phosphite of formula MONO-I-P,MONO-I-O or MONO-I-M, andd) a second further additive, which is a phosphite of formula PRE-I-P,PRE-I-O or PRE-I-M,whereinwhen component b) is of formula I-P, the further additive is a phosphiteof formula MONO-I-P and the second further additive is a phosphite offormula PRE-I-P, wherein the respective substituents at formula I-P, atformula MONO-I-P and at formula PRE-I-P are the same,when component b) is of formula I-O, the further additive is a phosphiteof formula MONO-I-O and the second further additive is a phosphite offormula PRE-I-O, wherein the respective substituents at formula I-O, atformula MONO-I-O and at formula PRE-I-O are the same,when component b) is of formula I-M, the further additive is a phosphiteof formula MONO-I-M and the second further additive is a phosphite offormula PRE-I-M, wherein the respective substituents at formula I-M, atformula MONO-I-M and at formula PRE-I-M are the same.

Accordingly, the additive mixture of the previous paragraph is also anexample of an additive composition, which comprises

b) a compound of formula I-P, I-O or I-M, andc) a further additive, which is a phosphite of formula PRE-I-P, PRE-I-Oor PRE-I-M, whereinwhen component b) is of formula I-P, the phosphite is of formulaPRE-I-P,wherein the respective substituents at formula I-P and at formulaPRE-I-P are the same,when component b) is of formula I-O, the phosphite is of formulaPRE-I-O,wherein the respective substituents at formula I-O and at formulaPRE-I-O are the same,when component b) is of formula I-M, the phosphite is of formulaPRE-I-M,wherein the respective substituents at formula I-M and at formulaPRE-I-M are the same.

An oxidizing agent can be chosen substoichiometrically for example byemploying for 1 mol of a compound of formula I-P, I-O or I-M an amountof the oxidizing agent, which results in less than 2 mol oxidativeoxygen-equivalent. Here, oxidative oxygen equivalent refers to theamount of an oxidizing agent, which is necessary to transform onephosphorous atom in formula PRE-I-P, PRE-I-O or PRE-I-M to therespective P═O group in the respective formula I-P, I-O or I-M. Forexample, for 1 mol of a compound of formula PRE-I-P, PRE-I-O or PRE-I-M,the amount of m-chloroperbenzoic acid is chosen to be 1.0 mol forobtaining an additive mixture. This example is the situation, where theamount of oxidizing agent in the process for manufacturing a compound offormula I-P, I-O or I-M is substoichiometrically chosen exactly inbetween stoichiometrically and zero.

A further embodiment of this invention relates to a further process formanufacturing a compound of formula I-P, I-O or I-M. The basic syntheticapproach for manufacturing is the reaction of a suitablehalogen-substituted phosphorous derivative with the respectivehydroxy-substituted benzofuran-2-one derivative in the presence of abase and optionally a solvent, especially an aprotic solvent.

Halogen is a fluorine atom, a chlorine atom, a bromine atom or a jodineatom. Preferred is a chlorine or a bromine atom, in particular achlorine atom.

Preferred is a further process, wherein the base is triethylamine,pyridine, potassium carbonate or sodium carbonate.

An aprotic solvent is for example acetonitrile, dichloroethane ortoluene.

Preferred is a further process for manufacturing a compound of formulaI-P

wherein

-   -   R^(1P) represents one of the subformulae II-P, II-O or II-M

R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen orC₁-C₈-alkyl,R^(P2), R^(P3), R^(P5) and R^(P6) are independently from each otherhydrogen or C₁-C₈-alkyl,R^(O1), R^(O2), R^(O5) and R^(O6) are independently from each otherhydrogen or C₁-C₈-alkyl, andR^(M1), R^(M3), R^(M5) and R^(M6) are independently from each otherhydrogen or C₁-C₈-alkyl,which comprises the steps of

-   -   reacting a compound of formula S-IN-P

with a compound of formula PS-IN-P

-   -   wherein Z^(1P-IN) and Z^(2P-IN) are independently from each        other halogen,        in the presence of a base and optionally an aprotic solvent to        obtain a compound of formula IN-P

-   -   reacting the compound of formula IN-P with a compound of formula        S1-IN-P

HO—R^(1P)  (S1-IN-P)

in the presence of a base and optionally an aprotic solvent to obtainthe compound of formula I-P, wherein R^(1P), R⁴, R⁵, R⁶, R⁷, R^(P2),R^(P3), R^(P5), R^(P6), R^(O1), R^(O2), R^(O5), R^(O6), R^(M1), R^(M3),R^(M5), R^(M6), Z^(1P-IN) and Z^(2P-IN) are at all formulae the ones offormulae I-P and PS-IN-P.

At the further process for manufacturing a compound of formula I-P, thestep of reacting a compound of formula S-IN-P with a compound of formulaPS-IN-P and the step of reacting a compound of formula IN-P with acompound of formula S1-IN-P can occur in parallel once a certain amountof compound IN-P is formed.

Preferred is a further process for manufacturing a compound of formulaI-O

wherein

-   -   R^(1O) represents one of the subformulae II-O or II-M

R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen orC₁-C₈-alkyl,R^(O1), R^(O2), R^(O5) and R^(O6) are independently from each otherhydrogen or C₁-C₈-alkyl, andR^(M1), R^(M3), R^(M5) and R^(M6) are independently from each otherhydrogen or C₁-C₈-alkyl,which comprises the steps of

-   -   reacting a compound of formula S-IN-O

with a compound of formula PS-IN-O

-   -   wherein Z^(1O-IN) and Z^(2O-IN) are independently from each        other halogen,        in the presence of a base and optionally an aprotic solvent to        obtain a compound of formula IN-O

-   -   reacting the compound of formula IN-O with a compound of formula        S1-IN-O

HO—R^(1O)  (S1-IN-O)

in the presence of a base and optionally an aprotic solvent to obtainthe compound of formula I-O,wherein R^(1O), R⁴, R⁵, R⁶, R⁷, R^(O1), R^(O2), R^(O5), R^(O6), R^(M1),R^(M3), R^(M5), R^(M6), Z^(1O-IN) and Z^(2O-IN) are at all formulae theones of formulae I-O and PS-IN-O.

At the further process for manufacturing a compound of formula I-O, thestep of reacting a compound of formula S-IN-O with a compound of formulaPS-IN-O and the step of reacting a compound of formula IN-O with acompound of formula S1-IN-O can occur in parallel once a certain amountof compound IN-O is formed.

Preferred is a further process for manufacturing a compound of formulaI-M

wherein

-   -   R^(1M) represents the subformula II-M

R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen orC₁-C₈-alkyl,R^(M1), R^(M3), R^(M5) and R^(M6) are independently from each otherhydrogen or C₁-C,which comprises the steps of

-   -   reacting a compound of formula S-IN-M

with a compound of formula PS-IN-M

-   -   Z^(1M-IN) and Z^(2M-IN) are independently from each other        halogen,        in the presence of a base and optionally an aprotic solvent to        obtain a compound of formula IN-M

-   -   reacting the compound of formula IN-M with a compound of formula        S1-IN-M

HO—R^(1M)  (S1-IN-M)

in the presence of a base and optionally an aprotic solvent to obtainthe compound of formula I-M,wherein R^(1M), R⁴, R⁵, R⁶, R⁷, R^(M1), R^(M3), R^(M5), R^(M6),Z^(1M-IN) and Z^(2M-IN) are at all formulae the ones of formulae I-M andPS-IN-M.

At the process for manufacturing a compound of formula I-M, the step ofreacting a compound of formula S-IN-M with a compound of formula PS-IN-Mand the step of reacting a compound of formula IN-M with a compound offormula S1-IN-M can occur in parallel once a certain amount of compoundIN-M is formed.

The formulae PS-IN-P, PS-IN-O and PS-IN-M are covering the samecompounds, but are individualized for clarity in the reaction schemesfor a compound of formula I-P, I-O or I-M. Furthermore, the formulaS1-IN-P is in case of subformula II-P for R^(1P) similar to the formulaS-IN-P. The formula S1-IN-P is in case of subformula II-O for R^(1P)similar to the formula S-IN-O. The formula S1-IN-P is in case ofsubformula II-M for R^(1P) similar to formula S-IN-M. The formulaS1-IN-O is in case of subformula II-O for R^(1O) similar to the formulaS-IN-O. The formula S1-IN-O is in case of subformula II-M for R^(1O)similar to the formula S-IN-M. The formula S1-IN-M is in case ofsubformula II-M for R^(1M) similar to the formula S-IN-M.

A further embodiment of this invention relates to an intermediatecompound of formula IN-P, IN-O or IN-M

whereinZ^(1P-IN), Z^(1O-IN) and Z^(1M-IN) are independently from each otherhalogen,R⁴, R⁵, R⁶ and R⁷ are independently from each other hydrogen orC₁-C₈-alkyl,R^(P2), R^(P3), R^(P5) and R^(P6) are independently from each otherhydrogen or C₁-C₈-alkyl,R^(O1), R^(O2), R^(O5) and R^(O6) are independently from each otherhydrogen or C₁-C₈-alkyl, andR^(M1), R^(M3), R^(M5) and R^(M6) are independently from each otherhydrogen or C₁-C₈-alkyl.

The following examples illustrate further the invention without limitingit. Percentage values are percentage by weight if not stateddifferently.

SYNTHETIC EXAMPLES

The synthetic procedures are conducted under a nitrogen atmosphere.

If not otherwise stated, the starting materials are commerciallyavailable, for example from Aldrich Corp.

Example S-1: Synthesis of Compound (102)

5.0 g (15 mmol) of compound (202) (obtainable according to EP 2500341 A,page 8, example 1 by using the corresponding 4-tert-octyl-phenol) aredissolved in 40 mL of dry dichloroethane at 65° C. To the solution arefirst added 1.41 g (18 mmol) of dry pyridine and then within 25 min 1.96g (7 mmol) of compound (301)(3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane,obtainable according to Lucas et al., Tetrahedron Lett. 2005, 46, 3347).The reaction mass is stirred under reflux for 3 h, cooled to roomtemperature and filtrated. After removal of solvent, a glassy residue isobtained which is further dried at 70° C. under vacuum. 5.3 g (69% oftheory) of compound (102) as an amorphous solid are obtained.

³¹P-NMR (toluene-d₈): 116 ppm

¹H-NMR (toluene-d₈): 4.3 ppm (s, 2H, CH at lactone-ring)

MS (LC/MS, ACPI positive mode): [M+1]⁺=1094

Example S-2: Synthesis of Compound (103)

Compound (103) is prepared in analogy to example S-1 from compound (203)(obtainable according to EP 0648765 A, page 30, compound 115) andobtained in a yield of 81% of theory as an amorphous solid.

³¹P-NMR (toluene-d₈): 122 ppm

¹H-NMR (toluene-d₈): 4.3 ppm (s, 2H, CH at lactone-ring)

MS (LC/MS, ACPI positive mode): [M+1]⁺=926

Example S-3a: Synthesis of Compound (402) with m-Perchlorobenzoic Acid

3.0 g (3.0 mmol) of compound (102) are dissolved in 40 mL of drydichloromethane and the solution is cooled to 5° C. 1.0 g (6 mmol) ofm-chloroperbenzoic acid are added in 2 portions. A yellowish precipitateis formed, which slowly dissolves again. The solution is stirred for 3 hat 5° C. After removal of the solvent, the solid residue is purified byflash chromatography (SiO₂, heptane/ethyl acetate 9:1). 2.7 g (89% oftheory) of compound (402) are obtained as a colorless amorphous solid.

³¹P-NMR (DCM-d₂): −15.1 ppm

¹H-NMR (DCM-d₂): 4.75 ppm (s, 2H, lactone-H)

MS (LC/MS, ACPI positive mode): [M+H]⁺=1125

Example S-3b: Synthesis of Compound (402) with Hydrogen Peroxide

2.7 g (2.5 mmol) of compound (102) are dissolved in 25 mL ofacetonitrile, the solution is cooled to 5° C. and 5 mL of 10% aqueoushydrogen peroxide (15 mmol) are added at this temperature. Afterappearance of an emulsion-like reaction mass a waxy productprecipitates, which is filtered off after 6 h of stirring andre-dissolved in 80 mL ethyl acetate. After treating this solution 2times with 50 mL of an aqueous solution of 20% NaHSO₃, the organic phaseis washed with 50 mL brine and dried over Na₂SO₄. After removing thesolvent, 2.2 g (91% of theory) of compound (402) is obtained in pureform as a colorless amorphous solid.

Analytical data as stated at example S-3a.

Example S-3c: Synthesis of Compound (402) by Condensation with Compound(501)

7.8 g (26 mmol) of compound (501), which is prepared by reaction ofpentaerythritol with phosphoryl chloride (═POCl₃) as described inPolymer Degradation and Stability, 2015, 113, p. 86-94, are dissolved in100 mL of dry acetonitrile at room temperature. 24.5 g (53 mmol) ofcompound (202) are added in 3 portions. A suspension is formed. 8.0 mL(57 mmol) triethylamine are added dropwise. After heating under refluxfor 16 h, the reaction mass is cooled to room temperature. Theprecipitated solids are filtered off and washed with 250 mL of water.After final washing with 150 mL acetonitrile at 0° C., the product isdried at 60° C. under vacuum. 17.3 g (59% of theory) of compound (402)is obtained as a colorless amorphous solid.

Analytical data as stated in example S-3a.

Example S-4a: Synthesis of Compound (403) with m-Perchlorobenzoic Acid

5.02 g (5 mmol) of compound (103) are dissolved in 30 mL of drydichloromethane and the solution is cooled to 5° C. 2.62 g of 70%m-chloroperbenzoic acid (10 mmol) are added in 2 portions. A colorlessprecipitate is formed. The suspension is stirred for 3 h at 5° C. Theprecipitate is filtered off and washed with additional 100 mL ofdichloromethane. The combined filtrates are evaporated to dryness andthe solid residue is purified by flash chromatography (SiO₂,heptane/ethyl acetate 9:1). 1.4 g (27% of theory) of compound (403) areobtained as a colorless amorphous solid.

³¹P-NMR (DCM-d₂): −12.9 ppm

¹H-NMR (DCM-d₂): 4.82 ppm (s, 2H, lactone-H)

MS (LC/MS, positive mode): [M+H]⁺=958

Example S-4b: Synthesis of Compound (403) with Hydrogen Peroxide

6.8 g (6.7 mmol) of compound (103) are dissolved in 60 mL ofacetonitrile and 15 mL of 10% hydrogen peroxide (45 mmol) are added atroom temperature. The mixture is heated to 40° C. and stirred at thistemperature for 150 min. After cooling to 20° C., the reaction mass isadded to 100 mL water of 0° C., the precipitated product is filtered offand dissolved in 100 mL ethyl acetate. After treating this solution twotimes with 50 mL of an aqueous solution of 20% NaHSO₃, the organic phaseis washed with 100 mL. brine and dried over Na₂SO₄. After removing thesolvent, the product is purified by flash chromatography (SiO₂,heptane/ethyl acetate 9:1). 5.0 g (72% of theory) of compound (403) areobtained as a colorless amorphous solid. Analytical data as in exampleS-4a.

APPLICATION EXAMPLES

The following known stabilizers are partly employed in addition to theinventive compounds:

AO-1 is Irganox 1010 (RTM BASF), which contains pentaerythritoltetrakisβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

AO-2 is Irganox 1076 (RTM BASF), which contains stearylβ-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

Phos-1 is Irgafos 168 (RTM BASF), which containstris(2,4-di-tert-butylphenyl) phosphite.

CaSt is commercially available calcium stearate, which acts as an acidscavenger.

For polymer processing at example A-1, the polymer of interest ingranular form is blended with various additives according to the recipeof the formulation as stated at the respective table. The blending iscarried out using Henschel, Turbula or Kitchen-Aid mixers. Thethoroughly blended formulations are then melt compounded in a twin-screwextruder at lower temperature (210° C. [410° F.]) under nitrogen. Thisensures good melt mixing with minimal damage to the polymer due tooxidative degradation. A zero pass extrudate is obtained, which isdenoted in the examples as the zero-pass extrusion.

The resultant zero pass extrudate at example A-1 is then extrudedmultiple times a single screw extruder, fitted with a Maddock mixingsection, at higher temperature (260° C. [500° F.]) and open to air.Extrusion at higher temperatures in combination with the presence ofoxygen (air) enhance the rate of polymer degradation. These aggressiveextrusion conditions put a strain on the stabilization system, whichallows for differentiation by various testing. This multiple passextrusion indicates processing stability. Pelletized samples of zero,first, third and fifth pass extrudate are collected and stored in sealedplastic bags at room temperature in storage boxes in the dark.

Melt flow rates of a samples at example A-1 are tested for retention ofmolecular mass (weight). This is measured by melt flow rate retention(according to ASTM-1238) on a Tinius-Olsen extrusion plastometer. For apolypropylene, the test conditions are 230° C. and 2.16 kg. Melt flowrates are measured in grams of polymer that flow out of a definedorifice in 10 minutes or decigrams/minute.

Oven aging of a sample at example A-1 is tested for oxidative stabilitybelow the melting point of the polymer and indicates post extrusion longterm thermal stability. Warming below the melting point of the polymeraccelerates polymer degradation. Oven aging is done by puttingcompression molded plaques (1 mm [40 mils]) in a Blue M forced draftoven equipped with a rotating carousel in order to homogenize theexposure to elevated temperatures (130° C., 150° C.) inside the oven.Failure is measured by days to embrittlement by bending the plaque every3 to 4 days until the plaque snapped due to oxidative degradation. Thetime is measured in days.

Oxidative induction time (OIT) at example A-1 is tested for oxidativestability above the melting point of the polymer and indicates postextrusion thermal stability. Oxidative induction time (OIT) is a meansof measuring the activity of the stabilizer in the polymer melt at hightemperatures (190° C.) and an oxidative environment (oxygen). Theexperiment is run on a differential scanning calorimeter (DSC). A scanis collected using a heating rate of 10° C./min under nitrogen from 50°C. to 190° C., then switching to oxygen and holding at isothermalconditions until catastrophic oxidation. Time to onset of catastrophicoxidation (observed as a strong exotherm) is measured in minutes. Thesample is tested in the form of a film with a thickness of 0.25 mm (10mils).

Yellowness Index (Yl) at example A-2 is tested for color change and ismeasured according to DIN 6167.

Example A-1: Stabilization of a Polypropylene Homopolymer

A commercially available molding grade Ziegler-Natta polypropylene(zn-PP-homopolymer) with a melt flow rate of 12 dg/min from abulk/slurry phase polymerization process, which is essentially free ofany stabilization additives, is processed and evaluated as described intable A-1.

TABLE A-1 composition No. 1 ^(a)) 2 ^(a)) 3 ^(a)) 4 ^(b)) 5 ^(b))zn-PP-homopolymer 99.99 99.85 99.80 99.8468 99.8675 CaSt 0.050 0.0500.050 0.050 0.050 AO-1 0.050 0.050 0.050 0.050 0.050 Phos-1 — 0.0500.100 0.0407 0.022 compound (403) — — — 0.0125 — compound (402) — — — —0.0105 total additives content 0.100 0.150 0.200 0.1532 0.1325phosphorus (III) ^(c)) — 0.0024 0.0048 0.0020 0.0011 260° C. (500° F.)melt processing melt flow rates zero pass 22.55 15.70 15.06 15.73 16.041^(st) pass 33.90 19.71 17.11 17.74 17.15 3^(rd) pass 51.52 25.66 20.0919.68 18.44 5^(th) pass 66.92 30.88 22.32 22.33 20.58 5^(th) pass lesszero 44.38 15.19 7.26 6.60 4.54 pass oven ageing zero pass/135° C. 18 7186 86 71 zero pass/150° C. 2 14 21 18 13 Oxidative induction time zeropass/190° C. 4 15 33 20 18 Footnotes: ^(a)) reference ^(b)) inventive^(c)) calculated based on phosphorus (III) [=P(III)] provided by Phos-1(4.8 parts by weight P(III) based on 100 parts oftris(2,4-di-tert-butylphenyl) phosphite; 100% content assumed) and basedon no contribution by compound (402) (5.5 parts by weight P(V) based on100 parts of compound (402); 100% content assumed) or by compound (403)(6.5 parts by weight P(V) based on 100 parts of compound (403); 100%content assumed)

The data of table A-1 show that

-   (i) a three-component mixture comprising compound (403) or    compound (402) keep melt flow rates during processing more stable    than a two-component mixture without compound (403) or    compound (402) at a comparable overall additives content and even at    a clearly lowered overall additives content;-   (ii) a three-component mixture including compound (403) or    compound (402) shows oven aging values and oxidation induction time    values comparable to a two-component mixture without compound (403)    or compound (402) at a comparable overall additive content;-   (iii) the findings of (i) and (ii) are obtained despite of a reduced    content of phosphorous (III), which is said to act as stabilizing    group by its reacting with oxygen to phosphorous (V), e.g. from a    phosphite to a phosphate; particularly the findings of (ii) are    obtained in long term exposure to air containing oxygen at oven    aging or at exposure to pure oxygen at oxidation induction time.

Example A-2: Stabilization of a Linear Low-Density Polyethylene

A commercially available linear low-density polyethylene (LL 6130 APfrom BP Chemicals, linear LDPE) in form of a polymer powder is mixedwith the stabilizers as provided in table A-2 in a highspeed mixer(Mixaco Lab CM2). The obtained mixture in powder form is compounded in atwin-screw extruder (Collin 25/42 D) at 210° C. under a nitrogen blanketand pelletized. The processing stability of these pellets isinvestigated via multiple pass extrusion under air with a single screwextruder at 240° C. Pellets after the first pass extrusion, third passextrusion and fifth pass extrusion are compression-molded to 2 mmplaques and the yellowness index is measured. Results are depicted intable A-2.

composition No. 2-1 ^(a)) 2-2 ^(b)) 2-3 ^(a)) 2-4 ^(b)) LL6163 AP (lin.LD-PE) 99.85 99.85 99.85 99.85 CaSt 0.050 0.050 0.050 0.050 AO-2 — —0.030 0.030 compound (403) — 0.100 — 0.070 compound (103) 0.100 — 0.070— total additives content 0.150 0.150 0.150 0.150 phosphorus (III) ^(c))0.0067 — 0.0047 — 240° C. melt processing yellowness index zero pass41.5 81.3 51.3 81.6 1^(st) pass 56.6 90.1 68.1 90.2 3^(rd) pass 70.194.0 70.1 95.4 5^(th) pass 76.3 95.1 87.7 97.5 delta yellowness index19.7 5.0 19.6 7.3 1^(st) pass vs 5^(th) pass Footnotes: ^(a)) reference^(b)) inventive ^(c)) calculated based on phosphorus (III) [=P(III)]provided by compound (103) (6.7 parts by weight P(III) based on 100parts of compound (103); 100% content assumed) and based on nocontribution by compound (403) (6.5 parts by weight P(V) based on 100parts of compound (403); 100% content assumed)

The data of table A-2 show that

-   (i) compound (403) provides a slower increase of yellowness index    than compound (103), i.e. a less changing yellowness index    respectively less change of the initial color after compounding;-   (ii) compound (403) in combination with AO-2 provides a more stable    yellowness index than compound (103) in combination with AO-2, i.e.    a less changing yellowness index respectively less change of the    initial color after compounding.

Example H-1: Hydrolytic Stability of Compound (402) and Compound (403)

Hydrolysis testing: A sample is tested for hydrolytic stability using aforced draft humidity oven with the proper adjustments to maintain 50°C. (122° F.) and 80% relative humidity. The test method involves putting0.5 grams of the material to be tested in properly labeled glass vials,uncapped. For the present testing, several sets of vials are providedand the samples are removed from the humidity oven every few days. Theexposed sample is then tested for the extent of hydrolysis by HighPressure Liquid Chromatography (HPLC), which measures the retention ofintact starting material as well as transformation chemistry. Theincrease of the presence of a hydrolysis product is used as an indicatorfor loss of intact starting material.

Compound (402) and compound (102) are tested for hydrolysis byobservation of the generation of content of compound (202) via thehydrolysis reaction.

Compound (403) and compound (103) are tested for hydrolysis byobservation of the generation of content of compound (203) via thehydrolysis reaction.

Sample H-1-I:

-   -   compound (402) in the form of a white powder    -   after 61 days, the sample H-1-I is still a free-flowing white        material

Sample H-1-II:

-   -   compound (102) in the form of white powder    -   after 10 days, the sample H-1-II is waxy to the touch and less        free-flowing

Sample H-1-III:

-   -   compound (403) in the form of a white powder    -   after 61 days, the sample H-1-III is still a free-flowing white        material

Sample H-1-IV:

-   -   compound (103) in the form of a white powder (with 5% already        liberated lactone moiety due to hydrolysis despite of a previous        storage in a dry desiccator at 20° C.; this hydrolytic        instability would require some type of hydrolysis inhibitor such        as the well-known tri-isopropanol amine)    -   after 7 days, the sample H-1-IV is waxy to the touch and less        free-flowing

TABLE H-1-1 Sample No. time of H-1-I ^(b)) H-1-II ^(a)) H-1-III ^(b))H-1-IV ^(c)) exposure content of compound (202) ^(c)) content ofcompound (203) ^(c)) [days] [area %] [area %] 0 1.1 0.2 0.0  5.0 3 1.10.4 0.0 — 4 — — 0.0  6.1 5 1.1 0.6 0.0 — 7 — — 0.0 13.0 10 — 9.9 0.043.7 14 1.0 100 0.1 — 15 — — — 90.0 30 1.1 — 0.2 — 45 1.0 — 0.2 — 61 0.9— 0.2 — Footnotes: ^(a)) reference ^(b)) inventive ^(c)) the content ofcompound (202) or compound (203) refers to the percent of libatedlactone moiety as a consequence of the hydrolysis reaction. Theanalytical method (HPLC) is evaluated so that it corrects for theabsorption coefficient for each of the starting products, as well as theproducts that are generated by the hydrolysis reaction. Accordingly,100% hydrolysis refers to 100% of the potential lactone moiety thatcould be liberated is actually liberated

All tested samples except for compound (103) start out intact with lessthan or around 1% of compound (202) respectively compound (203). After14 days, compound (102) is failed and after 15 days, compound (103) isessentially failed. In comparison, there is virtually no hydrolysis ofcompound (402) or compound (403). It is preferred that hydrolysis isreduced and the tested sample remains a free-flowing white material.This illustrates the advantage of a compound of formula I-P, formula I-Oor formula I-M as a class of powerful melt processing stabilizers withremarkable hydrolytic stability.

1. A composition, comprising: a) an organic material susceptible tooxidative, thermal or light-induced degradation, and b) a compound offormula I-P, I-O or I-M

wherein R^(1P) represents one of the subformulae II-P, II-O or II-M

R^(1O) represents one of the subformulae II-O or II-M, or R^(1M)represents the subformula II-M; R⁴, R⁵, R⁶ and R⁷ are independently fromeach other hydrogen or C₁-C₈-alkyl, R^(P2), R^(P3), R^(P5) and R^(P6)are independently from each other hydrogen or C₁-C₈-alkyl, R^(O1),R^(O2), R^(O5) and R^(O6) are independently from each other hydrogen orC₁-C₈-alkyl, and R^(M1), R^(M3), R^(M5) and R^(M6) are independentlyfrom each other hydrogen or C₁-C₈-alkyl.
 2. The composition according toclaim 1, wherein the organic material is a polymer, an oligohydroxycompound, a wax, a fat or a mineral oil.
 3. The composition according toclaim 2, wherein the organic material is a polymer, which is apolyolefin or a copolymer thereof, a polystyrene or a copolymer thereof,a polyurethane or a copolymer thereof, a polyether, which is obtainableby the polymerization of an epoxide, an oxetane or a tetrahydrofuran, ora copolymer thereof, a polyester or a copolymer thereof, a polycarbonateor a copolymer thereof, a poly(vinyl chloride) or a copolymer thereof, apoly(vinylidene chloride) or a copolymer thereof, a polysulfone or acopolymer thereof, a poly(vinyl acetate) or a copolymer thereof, apoly(vinyl alcohol) or a copolymer thereof, a poly(vinyl acetal) or acopolymer thereof, or a polyamide or a copolymer thereof.
 4. Thecomposition according to claim 1, wherein R⁴ and R⁶ are hydrogen, R⁵ andR⁷ are independently from each other hydrogen or C₁-C₈-alkyl, R^(P2) andR^(P6) are independently from each other hydrogen or C₁-alkyl, R^(P3)and R^(P5) are independently from each other hydrogen or C₁-C₄-alkyl,R^(O1) and R^(O6) are independently from each other hydrogen orC₁-C₈-alkyl, R^(O2) is hydrogen or C₁-alkyl, R^(O5) is hydrogen orC₁-C₄-alkyl, R^(M1) is hydrogen or C₁-alkyl, R^(M3) and R^(M5) areindependently from each other hydrogen or C₁-C₄-alkyl, and R^(M6) ishydrogen or C₁-C₈-alkyl.
 5. The composition according to claim 1,wherein the compound is of formula I-P or I-O, R^(1P) represents one ofthe subformulae II-P or II-O, and R^(1O) represents the subformula II-O.6. The composition according to claim 1, further comprising a) apolymer, which is a polyolefin or a copolymer thereof or a polystyreneor a copolymer thereof, and b) the compound is of formula I-P or I-O,wherein R^(1P) represents subformula II-P, R^(1O) represents subformulaII-O, R⁴ and R⁶ are hydrogen, R⁵ and R⁷ are independently from eachother hydrogen or C₁-C₈-alkyl, R^(O1) is hydrogen or C₁-C₈-alkyl,R^(O2), R^(O5) and R^(O6) are hydrogen, R^(P2) and R^(P6) are hydrogen,and R^(P3) and R^(P5) are independently from each other hydrogen orC₁-C₄-alkyl.
 7. The composition according to claim 1, comprisingcomponent b) in an amount of 0.0005% to 10% based on the weight ofcomponent a).
 8. The composition according to claim 1, comprising ascomponent c) a further additive.
 9. The composition according to claim8, comprising as component c) a further additive, which is a phosphiteor phosphonite different to component b), an acid scavenger, a phenolicantioxidant or an aminic antioxidant.
 10. The composition according toclaim 9, comprising as component c) a phenolic antioxidant, which is anester of p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid.
 11. Thecomposition according to claim 8, comprising as component d) a secondfurther additive, which is a phosphite or phosphonite different tocomponent b), an acid scavenger, a phenolic antioxidant or an aminicantioxidant; with the proviso that component d) is a different compoundthan component c).
 12. A process for protection of an organic materialsusceptible to oxidative, thermal or light-induced degradation,comprising: providing the organic material, and incorporating into orapplying onto the provided organic material a compound of formula I-P,I-O or I-M as defined in claim
 1. 13. The process according to claim 12,wherein the organic material is a polymer, wherein the incorporatinginto the polymer takes place and a part or the complete incorporatingtakes place at a temperature between 135° C. to 350° C.
 14. A method ofusing a compound of formula I-P, I-O or I-M as defined in claim 1 forstabilizing an organic material susceptible to oxidative, thermal orlight-induced degradation against degradation by oxidation, heat orlight.
 15. A compound of formula I-P, I-O or I-M

wherein R^(1P) represents one of the subformulae II-P, II-O or II-M

R^(1O) represents one of the subformulae II-O or II-M, or R^(1M)represents the subformula II-M; R⁴, R⁵, R⁶ and R⁷ are independently fromeach other hydrogen or C₁-C₈-alkyl, R^(P2), R^(P3), R^(P5) and R^(P6)are independently from each other hydrogen or C₁-C₈-alkyl, R^(O1),R^(O2), R^(O5) and R^(O6) are independently from each other hydrogen orC₁-C₈-alkyl, and R^(M1), R^(M3), R^(M5) and R^(M6) are independentlyfrom each other hydrogen or C₁-C₈-alkyl.
 16. An additive composition,comprising: b) a compound of formula I-P, I-O or I-M as defined in claim1, and c) a further additive, which is a phosphite or phosphonitedifferent to component b), an acid scavenger, a phenolic antioxidant oran aminic antioxidant.
 17. The additive composition according to claim16, further comprising as component c) a phenolic antioxidant, which isan ester of p-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid. 18.The additive composition according to claim 16, further comprising ascomponent d) a second further additive, which is a phosphite orphosphonite different to component b), an acid scavenger, a phenolicantioxidant or an aminic antioxidant; with the proviso that component d)is a different compound than component c).
 19. The additive compositionaccording to claim 18, further comprising as component d) a secondfurther additive, which is tris-(2,4-di-tertbutyl phenyl) phosphite. 20.An intermediate compound of formula IN-P, IN-O or IN-M

wherein Z^(1P-IN), Z^(1O-IN) and Z^(1M-IN) are independently from eachother halogen, R⁴, R⁵, R⁶ and R⁷ are independently from each otherhydrogen or C₁-C₈-alkyl, R^(P2), R^(P3), R^(P5) and R^(P6) areindependently from each other hydrogen or C₁-C₈-alkyl, R^(O1), R^(O2),R^(O5) and R^(O6) are independently from each other hydrogen orC₁-C₈-alkyl, and R^(M1), R^(M3), R^(M5) and R^(M6) are independentlyfrom each other hydrogen or C₁-C₈-alkyl.